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A new measurement protocol was used for microscopic chemical analysis of surface oxide films with lateral resolution of 1 μm. The native air-formed oxide and an anodic passive film on austenite and ferrite phases of a 25Cr-7Ni super duplex stainless steel were investigated using synchrotron hard X-ray photoemission electron microscopy (HAXPEEM). Pre-deposited Pt-markers, in combination with electron backscattering diffraction mapping (EBSD), allowed analysis of the native oxide on individual grains of the two phases and the passive film formed on the same area after electrochemical polarization of the sample. The results showed a certain difference in the composition of the surface films between the two phases. For the grains with (001) crystallographic face // sample surface, the native oxide film on the ferrite contained more Cr oxide than the austenite. Anodic polarization up to 1000 mV/_Ag/AgCl in 1M NaCl solution at room temperature resulted in a growth of the Cr- and Fe-oxides, diminish of Cr-hydroxide, and an increased proportion of Fe³⁺ species.